O-Allylation of phenols with allylic acetates in aqueous medium using a magnetically separable catalytic system. Amit Saha, John Leazer* and Rajender S.
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Supporting information for
O-Allylation of phenols with allylic acetates in aqueous medium using a magnetically separable catalytic system Amit Saha, John Leazer* and Rajender S. Varma* Sustainable Technology Division, National Risk Management Research Laboratory, U. S. Environmental Protection Agency, 26 West M.L.K. Dr., MS 443, Cincinnati, Ohio 45268, USA
General Consideration………………………………………………….2 General Procedure for synthesis of compounds………………………..2 1
H and 13C NMR spectra……………………………………………….3-14
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General Consideration All the reactions were carried out in refluxing water under open aerial atmosphere. All the reagents were purchased from Sigma-Aldrich Chemical Co. and were used directly without further any purification. NMR spectra were obtained using the Brucker AVANCE 300MHz spectrometer using CDCl3 as solvent. Chemical shifts (δ) are given in ppm relative to TMS, coupling constants (J) in Hz. IR spectra were taken on Perkin Elmer Spectrum 2000 FT-IR spectrometer. Reactions were monitored by thin layer chromatography. Elemental analyses of the products were performed on a Costech Analytical - ECS 4010 Elemental analyzer. Elemental analyses of the catalyst before as well as after the reactions were performed on a Perkin Elmer Optima 3300 DV ICP-AES. Five mg of each sample was dissolved in 2.5 mL of concentrated aqua regia and the volume was adjusted to 50 mL in a volumetric flask. This solution was then used for the elemental analysis. TEM micrographs were recorded on TEM; Philips, CM20 microscope at an operating voltage of 200 kV. The particles were dispersed in ethanol by ultrasonication, loaded on a carbon coated copper grid, and then allowed to dry at room temperature before recording the micrographs.
Synthesis of magnetic nano-ferrites FeSO4.7H2O (13.9 g) and Fe2(SO4)3 (20 g) were dissolved in 500 mL water in a 1000 mL beaker. Ammonium hydroxide (25%) was added slowly to adjust the pH of the solution to 10. The reaction mixture was then continually stirred for 1 h at 60 oC. The precipitated nanoparticles were separated magnetically, washed with water until the pH reached 7, and then dried under a vacuum at 60 oC for 2 h. This magnetic nano-ferrite (Fe3O4) was then used for further chemical modification.
Surface functionalization of nano-ferrites Nano-Fe3O4 (2 g) was dispersed in 25 mL water by sonication for 30 min. Dopamine hydrochloride (2 g) dissolved in 5 mL of water was added to this solution and again sonicated for 2 h. The aminefunctionalized nanomaterial was then precipitated using acetone, isolated by centrifugation, and dried under vacuum at 60 oC for 2 h.
Synthesis of [Fe3O4-Dopamine-Pd] catalyst Dopamine functionalized nano-ferrite (1 g) was dispersed in MeOH (25 mL) by stirring. PdCl2 (200 mg) was added slowly to the suspension and the solution was stirred for 10 min. Ammonium hydroxide (25%) was added drop wise to bring the pH of the medium 9. The mixture was stirred at room temperature for 24 h. The nano catalyst was separated out using an external magnet. It was washed with acetone for three times and was dried under vacuum at 60 oC for 2 h.
O-Allylation of phenols by allylic acetates using [Fe3O4-Dopamine-Pd] catalyst A mixture of phenol (1 mmol), allylic acetate (1 mmol), NaHCO3 (2 mmol) and Pd-catalyst (50 mg, 4.8 mol%) was taken in 2.5 mL of water. The aqueous reaction mixture was heated to reflux for required time period as indicated in Table 2. The progress of the reaction was monitored by TLC. Standard work-up with ethyl acetate followed by simple column chromatography provided the pure product. All products listed in Table 3 were known in the literature (except entry 6 and 11) and were identified by comparison 2
Electronic Supplementary Material (ESI) for Green Chemistry This journal is © The Royal Society of Chemistry 2011
of their FT-IR, 1H and 13C NMR with literature data. The products of entries 6 and 11, Table 3, were characterized by FT-IR, 1H and 13C NMR spectroscopy and elemental analysis.
O
Ph
Table 3, entry 1 1H NMR, CDCl 3
3
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O
Ph
Table 3, entry 1 13C NMR, CDCl 3
O
Ph
Table 3, entry 2 1H NMR, CDCl 3
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O
Ph
Table 3, entry 2 13C NMR, CDCl 3
5
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6
Electronic Supplementary Material (ESI) for Green Chemistry This journal is © The Royal Society of Chemistry 2011
O
Ph
Table 3, entry 4 1H NMR, CDCl 3
O
Ph
Table 3, entry 4 13C NMR, CDCl 3
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O
Table 3, entry 5 1H NMR, CDCl 3
O
Table 3, entry 5 13C NMR, CDCl 3
8
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Ph
O Cl
Cl
Table 3, entry 6 1H NMR, CDCl 3
Ph
O Cl
Cl
Table 3, entry 6 13C NMR, CDCl 3
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Ph
O Br
Table 3, entry 7 1H NMR, CDCl 3
Ph
O Br
Table 3, entry 7 13C NMR, CDCl 3
10
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11
Electronic Supplementary Material (ESI) for Green Chemistry This journal is © The Royal Society of Chemistry 2011
O
Table 3, entry 9 1H NMR, CDCl 3
O
Table 3, entry 9 13C NMR, CDCl 3
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O OMe
Table 3, entry 10 1H NMR, CDCl 3
O OMe
Table 3, entry 10 13C NMR, CDCl 3
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O Cl
Table 3, entry 11 1H NMR, CDCl 3
O Cl
Table 3, entry 11 13C NMR, CDCl 3
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